- A Concise Route to 2-Sulfonylacetonitriles from Sodium Metabisulfite
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A three-component reaction of aryldiazonium tetrafluoroborates, sodium metabisulfite, and 3-azido-2-methylbut-3-en-2-ol under mild conditions is described. By using abundant and cheap sodium metabisulfite as the sulfur dioxide surrogate, this protocol features good functional group compatibility, affording 2-arylsulfonylacetonitriles in moderate to good yields. The reaction proceeds smoothly at room temperature without the need of any catalysts or additives. Moreover, the synthetic utility of this method is demonstrated by the transformation of 2-arylsulfonylacetonitrile into 2-arylsulfonyl acetamide and 2-arylsulfonylethylamine. (Figure presented.).
- Yao, Yanfang,Yin, Ziqing,Chen, Weiyun,Xie, Wenlin,He, Fu-Sheng,Wu, Jie
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supporting information
p. 570 - 574
(2020/12/09)
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- Photoinduced synthesis of 2-sulfonylacetonitriles with the insertion of sulfur dioxide under ultraviolet irradiation
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Metal-free insertion of sulfur dioxide with aryl iodides and 3-azido-2-methylbut-3-en-2-ol under ultraviolet irradiation at room temperature is achieved, giving rise to 2-(arylsulfonyl)acetonitriles in moderate to good yields. Alkyl iodide is also workable under these conditions. This transformation proceeds smoothly under mild conditions with a broad substrate scope. Various functional groups are compatible including amino, ester, halo, and trifluoromethyl groups. No metal catalyst or additive is needed during the reaction process. Mechanistic studies show that under ultraviolet irradiation, an aryl radical is generated in situ from aryl iodide, which undergoes subsequent sulfonylation via the insertion of sulfur dioxide leading to arylsulfonyl radical intermediates. Then the arylsulfonyl radical reacts with 3-azido-2-methylbut-3-en-2-ol giving rise to the corresponding 2-(arylsulfonyl)acetonitrile.
- Zhou, Kaida,Liu, Jin-Biao,Xie, Wenlin,Ye, Shengqing,Wu, Jie
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supporting information
p. 2554 - 2557
(2020/03/10)
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- Inhibitors of the Diadenosine Tetraphosphate Phosphorylase Rv2613c of Mycobacterium tuberculosis
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The intracellular concentration of diadenosine tetraphospate (Ap4A) increases upon exposure to stress conditions. Despite being discovered over 50 years ago, the cellular functions of Ap4A are still enigmatic. If and how the varied Ap4A is a signal and involved in the signaling pathways leading to an appropriate cellular response remain to be discovered. Because the turnover of Ap4A by Ap4A cleaving enzymes is rapid, small molecule inhibitors for these enzymes would provide tools for the more detailed study of the role of Ap4A. Here, we describe the development of a high-throughput screening assay based on a fluorogenic Ap4A substrate for the identification and optimization of small molecule inhibitors for Ap4A cleaving enzymes. As proof-of-concept we screened a library of over 42, 000 compounds toward their inhibitory activity against the Ap4A phosphorylase (Rv2613c) of Mycobacterium tuberculosis (Mtb). A sulfanylacrylonitril derivative with an IC50 of 260 ± 50 nM in vitro was identified. Multiple derivatives were synthesized to further optimize their properties with respect to their in vitro IC50 values and their cytotoxicity against human cells (HeLa). In addition, we selected two hits to study their antimycobacterial activity against virulent Mtb to show that they might be candidates for further development of antimycobacterial agents against multidrug-resistant Mtb.
- G?tz, Kathrin H.,Hacker, Stephan M.,Mayer, Daniel,Dürig, Jan-Niklas,Stenger, Steffen,Marx, Andreas
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p. 2682 - 2689
(2017/10/27)
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- Reactivity, Selectivity, and Stability in Sulfenic Acid Detection: A Comparative Study of Nucleophilic and Electrophilic Probes
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The comparative reaction efficiencies of currently used nucleophilic and electrophilic probes toward cysteine sulfenic acid have been thoroughly evaluated in two different settings-(i) a small molecule dipeptide based model and (ii) a recombinant protein model. We further evaluated the stability of corresponding thioether and sulfoxide adducts under reducing conditions which are commonly encountered during proteomic protocols and in cell analysis. Powered by the development of new cyclic and linear C-nucleophiles, the unsurpassed efficiency in the capture of sulfenic acid under competitive conditions is achieved and thus holds great promise as highly potent tools for activity-based sulfenome profiling.
- Gupta, Vinayak,Paritala, Hanumantharao,Carroll, Kate S.
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p. 1411 - 1418
(2016/06/09)
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- A molybdenum based metallomicellar catalyst for controlled and selective sulfoxidation reactions in aqueous medium
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A surfactant based molybdenum system that exhibits catalytic activity for sulfoxidation reactions of various organic sulfides in aqueous medium has been developed and comprehensively characterized using IR, XRD, NMR, ESI-MS, DLS and TEM. The catalyst showcases remarkable selectivity for the preparation of both sulfoxides and sulfones in the range of good to excellent yields. Furthermore, the catalyst showed a high degree of tolerance towards various sensitive functional groups such as hydroxyl, acetal, aldehyde, amine, imine, oxime, cyano and alkene. the Partner Organisations 2014.
- Chakravarthy, Rajan Deepan,Ramkumar, Venkatachalam,Chand, Dillip Kumar
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p. 2190 - 2196
(2014/04/17)
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- Ionic liquid catalyzed one-pot synthesis of novel spiro-2-amino-3- phenylsulfonyl-4H-pyran derivatives
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A series of novel spiro-2-amino-3-phenylsulfonyl-4H-pyran derivatives were synthesized via the three component, one pot reaction of phenylsulfonylacetonitrile and 1,3-dicarbonyl compounds with isatins or acenaphthenequinone in ethanol with a novel basic ionic liquid 2-hydroxyethyl ammonium acetate [H3N+CH2CH2OH] [CH3COO-] (HEAA) as catalyst. HEAA was found to be a suitable and efficient catalyst for this condensation. This method has some distinct advantages such as mild reaction conditions, short reaction time, and environmental friendliness.
- Jin, Shuai-Shuai,Wang, Hong,Guo, Hong-Yun
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p. 2353 - 2356
(2013/06/26)
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- Synthesis and biological evaluation of triazolothienopyrimidine derivatives as novel HIV-1 replication inhibitors
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We identified a novel class of triazolothienopyrimidine (TTPM) compounds as potent HIV-1 replication inhibitors during a high-throughput screening campaign that evaluated more than 200,000 compounds using a cell-based full replication assay. Herein, we report the optimization of the antiviral activity in a cell-based assay system leading to the discovery of aryl-substituted TTPM derivatives (38, 44, and 45), which exhibited significant inhibition of HIV-1 replication with acceptable safety margins. These novel and potent TTPMs could serve as leads for further development.
- Kim, Junwon,Kwon, Jeongjin,Lee, Doohyun,Jo, Suyeon,Park, Dong-Sik,Choi, Jihyun,Park, Eunjung,Hwang, Jong Yeon,Ko, Yoonae,Choi, Inhee,Ju, Moon Kyeong,Ahn, Jiye,Kim, Junghwan,Han, Sung-Jun,Kim, Tae-Hee,Cechetto, Jonathan,Nam, Jiyoun,Ahn, Sujin,Sommer, Peter,Liuzzi, Michel,No, Zaesung,Lee, Jinhwa
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p. 153 - 157
(2013/02/23)
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- Highly atom-economic, catalyst- and solvent-free oxidation of sulfides into sulfones using 30% aqueous H2O2
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Highly atom-efficient oxidation of sulfides into sulfones under solvent- and catalyst-free reaction conditions using a 30% aqueous solution of H 2O2 at 75 °C is reported. A structurally diverse set of phenyl alkyl-, phenyl benzyl-, benzyl alkyl-, dialkyl-, heteroaryl alkyl- and cyclic sulfides were transformed into sulfones regardless of the aggregate state and electronic nature of the substituents. In spite of the heterogeneous reaction mixtures throughout the work, no difficulties with stirring and reaction progress were noted. In numerous cases, only 10 mol% excess of H 2O2 was used, thus contributing considerably to the high atom economy of the process. Some solid substrates required a variable excess of hydrogen peroxide; however, the reactions were performed strictly without organic solvents. The transformation was demonstrated to be amenable for scale-up with both liquid and solid sulfides. In addition, isolation and purification of the crude products can be simply done with only filtration and crystallization.
- Jereb, Marjan
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supporting information
p. 3047 - 3052,6
(2020/09/16)
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- Cyanuric chloride promoted oxidation of sulfides to sulfoxides or sulfones in the presence of hydrogen peroxide
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Aromatic and aliphatic sulfides are readily oxidized to sulfoxides or sulfones in high yield with 35% hydrogen peroxide in the presence of cyanuric chloride (CC) as an efficient activator. The oxidation of sulfides proceeds at room temperature and the corresponding sulfoxides or sulfones was selectively obtained by controlling the amounts of H2O2 and CC. Various sulfides possessing functional groups such as hydroxyl, methoxy, nitrile, aldehyde and olefinic double bond were successfully and selectively oxidized without affecting sensitive functionalities. [image omitted].
- Lakouraj, Moslem Mansour,Abdi, Hamid,Hasantabar, Vahid
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experimental part
p. 435 - 441
(2012/06/16)
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- TiO2 nanoparticles and Preyssler-type heteropoly acid modified nano-sized TiO2: A facile and efficient catalyst for the selective oxidation of sulfides to sulfones and sulfoxides
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A new and efficient synthetic method has been developed for the selective conversion of sulfides into their corresponding sulfones and sulfoxides using H2O2 in the presence of neat or Preyssler-type heteropoly acid modified nano-sized TiO2 as catalyst, respectively. The reaction was performed at room temperature with quantitative yields. The catalyst is reusable without significant loss of activity for the next oxidation reaction.
- Rahimizadeh, Mohammad,Rajabzadeh, Ghadir,Khatami, Seyed-Mola,Eshghi, Hossein,Shiri, Ali
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scheme or table
p. 59 - 64
(2010/09/04)
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- Catalytic enantioselective mannich-type reaction with β-phenyl sulfonyl acetonitrile
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Figure presented The organocatalytic addition of β-phenyl sulfonyl acetonitrile 1 to either N-Boc-protected α-amido sulfones or imines allowed the synthesis of enantioenriched α-unsubstituted β-amino nitriles through a Mannich-type reaction.
- Gonzalez, Pedro B.,Lopez, Rosa,Palomo, Claudio
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supporting information; experimental part
p. 3920 - 3922
(2010/08/06)
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- Phenylsulfonyl as a directing group for nitrile oxide cycloadditions and mCPBA epoxidations
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An unexpected selectivity trend in the nitrile oxide cycloaddition and epoxidation reactions of 4,4-disubstituted cyclopentenes is reported. A variety of facially distinct, 'X-' and 'Y-substituted' cyclopentenes were investigated.
- Butler, Jeffrey D.,Donald, Michael B.,Ding, Zhensheng,Fettinger, James C.,Kurth, Mark J.
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scheme or table
p. 5110 - 5112
(2009/12/01)
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- How iodide anions inhibit the phase-transfer catalyzed reactions of carbanions
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The inhibitory effect of iodide anions on the phase-transfer catalyzed reactions of carbanions generated in liquid-liquid two-phase systems by aqueous NaOH is due to preferential location of these anions in the interfacial region of the two-phase system-organic phase/concd aqueous NaOH. In such situation, the basic activity of NaOH in this region is decreased and the equilibrium of deprotonation of the carbanion precursors is disfavoured.
- Makosza, Mieczys?aw,Chesnokov, Alexey
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p. 5925 - 5932
(2008/12/20)
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- Photolysis of open-chain 1,2-diazidoalkenes: generation of 2-azido-2H-azirines, formyl cyanide, and formyl isocyanide
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Solutions of several open-chain 1,2-diazidoethenes were photolyzed to yield 2-azido-2H-azirines, which were identified by NMR spectroscopy at low temperature. On prolonged irradiation or warm-up of the NMR solutions, these heterocycles lost a second molecule of nitrogen to be cleaved into two fragments of cyano compounds. In the case of (Z)-2,3-diazidocinnamaldehyde, the formation of formyl cyanide was detected by IR spectroscopy when the photolysis was performed in argon matrix. The latter substance was rearranged to formyl isocyanide on irradiation. This new species was characterized by comparison of its experimental and calculated (B3LYP/6-311+G**) IR spectrum.
- Banert, Klaus,Fotsing, Joseph Rodolph,Hagedorn, Manfred,Reisenauer, Hans Peter,Maier, Günther
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p. 5645 - 5648
(2008/09/21)
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- N-sulfonylbenzotriazoles as advantageous reagents for C-sulfonylation
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Reactions of readily available N-(alkyl-, aryl-, and heteroarylsulfonyl) benzotriazoles 3a-h with diverse nitriles, reactive heteroaromatics, alkylheteroaromatics, sulfones, and esters produced α-cyanoalkyl sulfones 5a-i, sulfonylheteroaromatics 7a-e, α-(sulfonylalkyl)heterocycles 9a-f, α-sulfonylalkyl sulfones 11a-g, and esters of α-sulfonyl acids 14a-c, respectively, in synthetically useful to excellent yields. The results represent the first examples of the successful application of sulfonylazoles for C-sulfonylation.
- Katritzky, Alan R.,Abdel-Fattah, Ashraf A. A.,Vakulenko, Anatoliy V.,Tao, Hui
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p. 9191 - 9197
(2007/10/03)
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- Preparation of Trifluoromethylated Pyrazoles and 1,4-Thiazine 1,1-Dioxides from Trifluoromethylated Sulfone Derivatives
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Trifluoromethylated sulfones, 3-amino-2-arylsulfonyl-4,4,4-trifluoro-3-hydroxybutanenitrile (3) and 3-(aroylmethyl)sulfonyl-1,1,1-trifluoropropane-2,2-diols 12, were prepared and cyclized to 4-arylsulfonyl-5-trifluoromethyl-3-hydrazinopyrazoles 9 and 5-arylsulfonyl-3-trifluoromethyl-3-hydroxy-2,3-dihydro-4H-1,4-thiazine 1,1-dioxides 13, respectively.
- Takahashi, Masahiko,Chigira, Keiko
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p. 207 - 210
(2007/10/02)
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- Alkylation of Sodium Phenylsulfinate on Alumina. Activation by Microwaves or Ultrasounds.
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Organic halides absorbed without solvent onto sodium phenylsulfinate on alumina (1) gave phenylsulfones (2) under microwave or ultrasound activation.
- Villemin, Didier,Alloum, Abdelkrim Ben
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p. 925 - 932
(2007/10/02)
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- A Novel Synthesis of Sulfones via the O,O-Diethylphosphorotellurite Ion-Assisted Coupling of Arenesulfonyl Chlorides with Active Halides
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Arenesulfonyl chlorides undergo a facile onepot coupling reaction with active halides assisted by sodium O,O-diethylphosphorotellurite to give the corresponding sulfones in excellent yield.
- Huang, Xian,Pi, Jin-Hong
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p. 2291 - 2295
(2007/10/02)
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- Synthesis of α-Arylated Phenylsulfonylacetonitriles. A Useful Precursor for Substituted α-Arylalkanoic Acid and Their Derivatives
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Copper(I) iodide-catalyzed reaction of aryl iodides with anion derived from phenylsulfonylacetonitrile in hot hexamethylphosphoric triamide affords α-arylated nitriles in good to moderate yields.Further alkylation of these nitriles followed by reductive removal of sulfonyl group provides a simple route to α-arylalkanenitriles.
- Suzuki, Hitomi,Yi, Qui,Inoue, Junko,Kusume, Kumiko,Ogawa, Takuji
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p. 887 - 890
(2007/10/02)
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- Organic Syntheses without Solvent: Preparation of Sulfones and Dithioacetals
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Sulfones are prepared by alkylation of sulfinate salts under solid-liquid phase-transfer catalysis without solvent; dithioacetals are obtained by heterogeneous uncatalyzed reactions of potassium arenethiolates and gem-dihaloalkanes.In both cases, the yields are high and the reaction conditions are mild.Some limitations are given.
- Bram, Georges,Loupy, Andre,Roux-Schmitt, Marie Claude,Sansoulet, Jean,Strzalko, Tekla,Seyden-Penne, Jacqueline
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- Preparation of 1,5-Disubstituted 4-Sulfonylpyrazoles, β-Cyano-β-sulfonylenamines and 5-Substituted 4-Sulfonylisoxazoles from β-Keto-β-sulfonylenamines
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Reaction of β-keto-β-sulfonylenamines 1a,b with N-substituted hydrazines gave 1,5-disubstituted 4-sulfonylpyrazoles 2a-h in moderate yields, which were ring-opened on treatment with n-butyllithium to afford β-cyano-β-sulfonylenamines (3a,b,d-f). 5-Substituted 4-sulfonylisoxazoles 6a-d were also prepared from 1a-d and hydroxylamine.
- Takahashi, Masahiko,Mamiya, Tsutomu,Hasegawa, Hisao,Nagai, Takashi,Wakita, Hideki
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p. 1363 - 1366
(2007/10/02)
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- Thio and sulfonyl glyoxylnitrileoxime phosphates and phosphonates
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Compounds of the formula EQU1 in which R is lower alkyl; R1 is lower alkyl or lower alkoxy; X is thio or sulfonyl; R2 is alkyl, benzothiazolo, benzyl, naphthyl, benzodiazolo-1,3, thiazolo, phenyl or substituted phenyl wherein said substituents are chloro, bromo, methyl or methoxy and the use of these compounds as insecticides.
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